JPWO2014163035A1 - Coated glass substrate and method for producing the same - Google Patents

Abstract

An object of the present invention is to provide a glass substrate that has good adhesion to a resin that is a black matrix material, has high resolution, and can reduce manufacturing control and cost burden. A coated glass substrate 1 having a coating 3 made of a cationic surfactant having a hydrophobic group having 14 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million on the surface of the glass substrate 2. By providing this film, the adhesion between the glass substrate and the resin material can be improved, and the resolution by the photolithography process can also be improved.

Description

  The present invention relates to a glass substrate with a coating and a method for producing the same, and more particularly to a glass substrate with a coating having a coating for improving the resin adhesion on the surface of the glass substrate and a method for producing the same.

  A substrate used for a color liquid crystal display usually forms a black matrix having a light shielding layer in a matrix form on a transparent glass plate in order to prevent light from leaking from between pixels. Further, a color filter layer is provided in a region to be a pixel, and an overcoat layer (usually using an organic resin) for further planarizing the surface is provided on the color filter layer. An ITO transparent conductive film is provided on the surface of the overcoat layer. The black matrix has a role of improving display characteristics by suppressing light leaking from outside the pixel effective area.

  In recent years, resin materials have come to be used as the black matrix, and in this case, the black matrix is generally formed by patterning using a photolithography technique. However, due to the small interaction between the resin black matrix and the transparent glass substrate forming the black matrix, the adhesion may be insufficient, and the black matrix may be locally peeled off during the patterning process. was there. Therefore, the production yield of the liquid crystal display is reduced, or the production process conditions are strictly controlled to increase the labor and the manufacturing cost in order to suppress the peeling.

  In order to solve such problems, for example, in order to improve the interaction between the resin material and the glass substrate to improve the adhesion, an organic functional group is added to the glass substrate, or a silicon dioxide film is formed. The method of doing is known (refer patent documents 1-3).

Japanese Patent Laid-Open No. 2000-212485 JP 2000-302487 A JP 2001-192235 A

  However, as the color liquid crystal display becomes higher in definition, a fine pattern is required to be formed by a black matrix. That is, there has been a demand for a glass substrate that can more effectively suppress peeling at the time of patterning the black matrix and that can also suppress the management and cost burden during manufacturing.

  Therefore, in order to solve the above-mentioned problems in conventional color liquid crystal display substrates, the present invention has good adhesion to the resin that is the black matrix raw material, high resolution, and the burden of manufacturing management and cost. It aims at providing the glass substrate which can reduce.

  The coated glass substrate of the present invention is a glass substrate in which a resin region is formed on the substrate, and a cationic surfactant or an average molecular weight having a hydrophobic group having 14 or more carbon atoms on the surface of the glass substrate. Has a film made of 5 to 10 million cationic polymers.

  Moreover, the manufacturing method of the glass substrate with a film of this invention contains the cationic surfactant which has a C14 or more hydrophobic group on the surface of a glass substrate, or a cationic polymer with an average molecular weight of 5-10 million. It has a step of forming a film made of the cationic surfactant or the cationic polymer by contacting and drying the solution.

  According to the glass substrate with a film and the method for producing the same of the present invention, a film that improves adhesion to the resin material is provided on the surface of the glass substrate, and the resin material can be stably formed on the glass surface. In particular, a black matrix can be formed stably during the manufacture of a color liquid crystal display. In addition, the glass substrate provided with this coating can improve the resolution of black matrix formation, and can stably produce a high-definition liquid crystal display.

It is sectional drawing which shows schematic structure of the glass substrate with a film of this invention. It is the figure which showed the contact angle with the pure water of the glass substrate of an Example and a comparative example. It is the graph which showed the relationship between the contact angle with the pure water of the glass substrate of an Example and a comparative example, and residual resolution.

  The coated glass substrate of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view showing a schematic configuration of a glass substrate with a coating according to the present invention. A glass substrate 1 with a coating according to the present invention is composed of a glass substrate 2 and a coating 3 formed on the surface thereof. .

  The glass substrate 2 used here is not particularly limited as long as it is a glass substrate that forms a resin region on its surface. As this glass substrate 2, what has a transparent and flat surface is preferable, for example, the glass substrate for color liquid crystal displays which forms resin-made black matrices etc. on the surface is mentioned as a preferable thing.

  Examples of the material of the glass substrate 2 include silicon dioxide, aluminum oxide, boron oxide, alkali metal oxides, alkaline earth metal oxides, and the like. In particular, borosilicate-based materials mainly composed of silicon dioxide and boron oxide. Preferable examples include alkali-free glass and soda lime silica glass mainly composed of silicon dioxide, sodium oxide and calcium oxide.

  The coating 3 used in the present invention is a single-layered film provided on the surface of the glass substrate 2. Here, the film 3 is a film composed of a cationic surfactant having a hydrophobic group having 14 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10,000,000.

  The cationic surfactant used here is not particularly limited as long as it is a cationic surfactant having a hydrophobic group having 14 or more carbon atoms. The cationic surfactant may be either an amine salt type or a quaternary ammonium salt type. For example, a trimethylammonium salt such as tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride; And pyridinium salts such as decylpyridinium, hexadecylpyridinium chloride, and octadecylpyridinium chloride. With this cationic surfactant, the adhesion between the resin material and the glass substrate can be improved.

  The cationic polymer used here may be a polymer having an average molecular weight of 500 to 10,000,000 and having a cationic group in the molecule. In addition, in this specification, an average molecular weight means a weight average molecular weight.

  Examples of the cationic polymer used here include polydiallyldimethylammonium chloride (PDAC or PDADMAC), poly (dimethylaminoethyl acrylate methyl chloride quaternary salt), poly (dimethylaminoethyl methacrylate methyl chloride quaternary salt), trimethylammonium. Examples include alkyl acrylamide polymer salts, dimethylamine epichlorohydrin condensate salts, polyallylamine, polyethyleneimine, and the like.

  The cationic polymer preferably has 4 to 25 cationic groups per 1000 molecular weight. The cationic group is a group that becomes a cation when dissolved in a solvent such as water, and examples thereof include an amino group and a quaternary ammonium group. At this time, the amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary amine, or secondary amine, and forms a primary amine, secondary amine, or tertiary amine, respectively. The quaternary ammonium group forms a quaternary ammonium cation.

  The coating 3 has a single layer structure, and has a function of improving the adhesion with the resin material on the glass surface while the manufacturing operation is simple and the structure is simple. The film 3 formed here is made of a surfactant and is bonded to the surface of the glass substrate by electrostatic bonding, and can be easily removed by washing with pure water or an alkaline detergent.

Next, the manufacturing method of the glass substrate with a film is demonstrated.
As a method for forming the coating 3 in the present invention, a solution containing a cationic surfactant having a hydrophobic group having 14 or more carbon atoms or a cationic polymer having an average molecular weight of 500 to 10 million on the surface of the glass substrate 2. May be contacted and dried to form a film made of a cationic surfactant or a cationic polymer.

  At this time, the cationic surfactant or the cationic polymer is dissolved in a pure water or an aqueous solution of a water-soluble organic solvent such as ethanol as a solvent to obtain a solution. At this time, the concentration (equivalent) of the cationic group is preferably from 0.01 meq / L to 100 meq / L, and more preferably from 0.1 to 10 meq / L so as not to become excessive while appropriately covering the glass product surface. Incidentally, when 1 mol of a cationic group is contained in 1 L of the solution, the concentration is expressed as 1 eq / L. The pH of the solution can be used from acidic to alkaline (for example, about pH 4 to 12), but the electrostatic bond strength is further strengthened by promoting the ionization of the silanol group on the glass surface and negatively charging it. However, the pH of the solution is preferably 8 to 12 and more preferably 10 to 11 in terms of increasing the adhesion amount.

  The solution thus obtained is applied in contact with the surface of the glass substrate on which the film is to be formed. At this time, the coating method includes a coating method used in a known film forming method of coating by dip coating, spray coating, sponge or the like. Further, in this step, the cationic surfactant or cationic polymer contained in the solution can be brought into contact with the cationic group so that the hydrophilic group of the cationic surfactant or the cationic portion of the cationic polymer is placed on the surface side of the glass substrate. Alignment is toward an atmosphere in which the main chain portion of the polymer that connects the hydrophobic group of the surfactant or the cationic portion of the cationic polymer is on the opposite side. This is because the silanol group (-Si-OH) present on the surface of the glass substrate is easily charged to -charge, so that the hydrophilic group or cationic polymer of the cationic surfactant charged with + charge only by contact is obtained. This is because the cationic portion is electrostatically attracted to the surface side of the glass substrate.

  When the solvent is removed by heating, air blowing or the like in the state where the cationic surfactants or the cationic polymers are aligned in this way, a homogeneous first film can be easily formed. At this time, in heat drying, it is preferable to heat to 50-90 degreeC, and in air blow, it is preferable to spray 15-30 degreeC air.

  Moreover, when forming this film, it can be achieved by a simple operation of applying the solution at room temperature, and further, surface modification of the glass substrate can be achieved without compromising drainage regulations and without increasing the environmental load. .

  And the glass substrate with a film obtained in this way can form the resin area | region stably through the film on the surface. Therefore, when the resin region is formed on the substrate surface, a product with high accuracy of the resin region and good yield can be manufactured.

  For example, when manufacturing a color liquid crystal display, prepare a transparent glass substrate of borosilicate non-alkali glass or soda lime silica glass, and form the above film on the surface to form a glass substrate with a film Then, a resin black matrix, a color filter layer, an overcoat layer, and an ITO transparent conductive film may be sequentially provided on the glass substrate via the coating film.

  Here, as the resin black matrix, a resin in which a black substance such as fine carbon is dispersed and mixed in an acrylic resin, an epoxy resin, a polyimide resin, a polyester resin or the like that can form a pattern with high dimensional accuracy is used. Form a black matrix. The color filter layer may also be formed of a known material used for a color liquid crystal display by a known method such as a pigment dispersion method, a film transfer method, a dyeing method, a printing method, or an electrodeposition method.

  Further, the overcoat layer is provided to flatten the unevenness generated at the boundary of R, G, B of the color filter layer provided on the resin black matrix, such as acrylic resin, epoxy resin, polyimide resin, etc. These may be formed by a known method. Furthermore, an ITO transparent electrode film may be formed by a known method.

  Since the color liquid crystal display thus obtained uses the glass substrate with a film of the present invention, the resin such as a black matrix is hardly peeled off during production and use, the product yield is good, and the performance It will be stable.

  Hereinafter, the present invention will be described in more detail based on examples and comparative examples.

[Preparation of various solutions]
<Solution 1 for film formation>
Each component was dissolved in pure water so that the concentration of octyltrimethylammonium chloride, which is a cationic surfactant, was 2 mmol / L and ammonia was 10 mmol / L to prepare a solution 1 for film formation. The pH of this solution is about 10.5.
<Solution 2 for film formation>
Each component was dissolved in pure water so that the concentration of decyltrimethylammonium chloride as a cationic surfactant was 2 mmol / L and ammonia was 10 mmol / L to prepare a solution 2 for film formation. The pH of this solution is about 10.5.

<Solution 3 for film formation>
Each component was dissolved in pure water so that the concentration of dodecyltrimethylammonium chloride, which is a cationic surfactant, was 2 mmol / L and ammonia was 10 mmol / L, thereby preparing a solution 3 for film formation. The pH of this solution is about 10.5.
<Solution 4 for film formation>
Each component was dissolved in pure water so that the concentration of tetradecyltrimethylammonium chloride as a cationic surfactant was 2 mmol / L and ammonia was 10 mmol / L to prepare a solution 4 for film formation. The pH of this solution is about 10.5.

<Solution 5 for film formation>
Each component was dissolved in pure water so that the concentration of hexadecyltrimethylammonium chloride, which is a cationic surfactant, was 2 mmol / L and ammonia was 10 mmol / L, thereby preparing a solution 5 for film formation. The pH of this solution is about 10.5.
<Solution 6 for film formation>
Each component was dissolved in pure water so that the concentration of octadecyltrimethylammonium chloride as a cationic surfactant was 2 mmol / L and ammonia was 10 mmol / L to prepare a solution 6 for film formation. The pH of this solution is about 10.5.

<Solution 7 for film formation>
Each component was dissolved in pure water so that the concentration of hexadecylpyridinium chloride (CPC), which is a cationic surfactant, was 2 mmol / LM and ammonia was 10 mmol / L to prepare a solution 7 for film formation. did. The pH of this solution is about 10.5.

<Solution 8 for film formation>
The polydiallyldimethylammonium chloride cationic polymer (PDAC or PDADMAC; colloid titration standard solution manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 60,000 to 110,000) is 2 meq / L and ammonia is 10 mmol / L. Each component was dissolved in pure water to prepare a solution 8 for film formation. The pH of this solution is about 10.5.

(Comparative Example 1)
A surface-polished glass plate made of non-alkali borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was dipped in the solution 1 for film formation for 10 seconds and then pulled up. A film was formed on the surface of the glass plate by a dip coating method that was dried by air blow to obtain a glass substrate with a film.

(Comparative Examples 2-3)
A glass with a coating is prepared in the same manner as in Comparative Example 1 except that the solution 2 for film formation (Comparative Example 2) or the solution 3 for film formation (Comparative Example 3) is used instead of the solution 1 for film formation. A substrate was manufactured.

Example 1
A surface-polished glass plate made of alkali-free borosilicate glass having a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm was dipped in the solution 4 for film formation for 10 seconds and then pulled up. A film was formed on the surface of the glass plate by a dip coating method that was dried by air blow to obtain a glass substrate with a film.

(Examples 2 to 5)
Instead of the film forming solution 4, the film forming solution 5 (Example 2), the film forming solution 6 (Example 3), the film forming solution 7 (Example 4), or the film forming solution A coated glass substrate was produced in the same manner as in Example 1 except that Solution 8 (Example 5) was used.

(Test example)
The contact angle of water on the surface of the glass substrate on which the film was not formed, the glass substrates of Examples 1 to 5 and Comparative Examples 1 to 3 was measured, and the results are shown in FIG. From this result, it was found that the water repellency is improved by increasing the number of carbon atoms of the hydrophobic group of the formed film. When a cationic polymer is applied, the contact angle is slightly reduced because some cationic groups are directed to the opposite side of the glass.
In addition, a predetermined photoresist patterning was formed on the surface of the glass substrate on which the film was not formed, the glass substrates of Examples 1 to 5 and Comparative Example 3, respectively, and the remaining resolution test was performed. The result is shown in FIG. Indicated. From this result, in Examples using a cationic surfactant and a cationic polymer in which the number of carbon atoms of the hydrophobic group is 14 or more, the remaining resolution is improved, the adhesion of the resin to the glass substrate is improved, and the stability is improved. As a result, it was found that a high-definition color liquid crystal display can be manufactured. In addition, when the number of carbon atoms of the hydrophobic group of Comparative Example 3 was 12, the resolution was comparable to that of a glass substrate without a film, and there was almost no improvement in resolution.

  In addition, sodium lauryl sulfate as an anionic surfactant and Triton X-100 (polyethylene glycol p octyl phenyl ether) as a nonionic surfactant are subjected to a film formation treatment on a glass substrate in the same manner as described above, and the remaining resolution is obtained. Although the test was conducted, the remaining resolution was the same as that of the glass substrate on which no film was formed.

[Contact angle]
One drop of pure water is dropped on the surface of the glass substrate to be measured, and the contact angle with the pure water on each substrate is averaged by averaging the five measurement results based on data obtained by imaging the water droplets on the surface from the side of the substrate. Calculated.

[Remaining resolution]
A negative photoresist is applied on the surface of the glass substrate to be measured, and potassium hydroxide (photolithographic process is used so that the resist width becomes 2 μm, 5 μm, 7 μm, 9 μm, 10 μm, 13 μm, 15 μm, and 20 μm). The development was performed with KOH), and the resolution was determined by leaving the minimum line width of the resist that remained on the glass substrate without peeling.

  From these results, the coated glass substrate of the present invention can adjust the water repellency to the glass substrate, improve the adhesion of the resin to the glass substrate, and the remaining resolution is good, and a fine pattern can be formed. I found it possible.

  The coated glass substrate of the present invention and the method for producing the same can be widely applied to a glass substrate, the size of the characteristics can be adjusted according to the number of carbons of the hydrophobic group to be used, and the material can be appropriately selected according to the purpose of use. Can produce a glass substrate with an optimum coating. The present invention is particularly suitable for a glass substrate used for a color liquid crystal display.

Claims (7)

A glass substrate in which a resin region is formed on a substrate,
A glass substrate with a coating, characterized by having a coating made of a cationic surfactant having a hydrophobic group having 14 or more carbon atoms or a cationic polymer having an average molecular weight of 5 to 10 million on the surface of the glass substrate.   The glass substrate with a coating according to claim 1, wherein the hydrophobic group of the cationic surfactant has 16 to 18 carbon atoms.   The coated glass substrate according to claim 1, wherein the cationic polymer has 4 to 25 cationic groups per 1000 molecular weight.   The glass substrate with a coating according to any one of claims 1 to 3, wherein the glass substrate with a coating has a contact angle with pure water of 20 to 90 degrees.   The glass substrate with a film according to any one of claims 1 to 4, wherein the glass substrate is for a color liquid crystal display.   A cationic surfactant having a hydrophobic group having 14 or more carbon atoms or a solution containing a cationic polymer having an average molecular weight of 5 to 10 million is contacted and dried on the surface of a glass substrate, and the cationic surfactant is obtained. Or the manufacturing method of the glass substrate with a film characterized by having the process of forming the film which consists of said cationic polymer.   The manufacturing method of the glass substrate with a film of Claim 6 whose solution used when forming the said film is aqueous solution of pH 8-12.

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